Thiosulfatoethyl sulfones

ABSTRACT

Certain thiosulfatoalkyl-alkoxyalkyl sulfones useful as modifiers of polymeric substrates are disclosed.

United States Patent 1 [111 3,764,619

Tesoro et al. Oct. 9, 1973 1 THIOSULFATOETHYL SULF ONES [75] Inventors:Giuliana C. Tesoro, Dobbs Ferry; [56] Reerences Cited Andrew Oroszlan,Elmhurst, both of V UNITED STATES PATENTS 3,201,434 8/1965 TBSOIO260/453 R 3,338,883 8/1967 Tesoro et a1. 260/453 R [73.] Assgnee'Stevens New 2,897,223 7/1959 Gaertner 260/453 R 2,934,552 4/1960Gaertner 260/453 R [22] Filed: Mar, 22, 1971 2,927,126 3/1960 Pursglove3,398,180 8/1968 Goldberg et al. 260/453 R [21] App]. No.: 126,867

Related U.S. Application D t Primary Examiner-Lewis Gotts [60] Divisionof Ser. No. 227,717, Oct. 2, I962, Assmam Humh abandoned, which is acontinuation-in-part of Set. Attorney-Bevendge & DeGl-andl No. 165,017,Jan. 8, 1962, Pat. No. 3,419,566.

[57] ABSTRACT Certain thiosulfatoalkyl-alkoxyalkyl sulfones useful asmodifiers of polymeric substrates are disclosed.

[52] US. Cl. 260/453 R, 260/460, 260/488 H, 260/594 [51] Int. Cl C0lb17/64 [58] Field of Search 260/453 R 1 Claim, No Drawings 1THIOSULFATOETHYL SULFONES The present application is a divisional ofapplication Ser. No. 227,717, filed Oct. 2, 1962 and now abandoned,which application is a continuation-in-part of application Ser. No.165,017, filed Jan. 8, 1962, now US. Pat. No. 3,419,566.

This invention relates to a method of stepwise modifying polymericmaterials with a polyfunctional reactant in which the functional groupshave different reactivity, and to the resulting modified materials soproduced; and, more particularly, to a method of crosslinking polymericmaterials with the aforementioned polyfunctional reactant wherein onefunctional group reacts with the polymeric material under one set ofreaction conditions and a second functional group reacts subsequentlywith the material under a difierent set of reaction conditions, and tothe cross-linked materials so produced. The invention further relates toa new and improved group of polyfunctional reactants and the method ofmaking the same.

The modification of polymeric materials to improve particular propertiesby treating the materials with a polyfunctional reactant is well known.One example is the cross-linking of linear polymers to form athreedimensional network. Thus, cellulosic textiles have beencross-linked with polyfunctional sulfones, epoxides, N-methylol amides,and the like, in order to modify the properties of the textiles,including those of dimensional stability, resilience, flat-drying, andthe like, which properties are not possessed by the textiles in theunmodified state. All of the cross-linking reagents which have been usedto date have similar functional groupings, and thus, while thecross-linking process does permit some control of the extent and rate ofthe reaction by adjusting concentrations, catalysts, temperatures, andthe like, it is generally impossible to exercise sufficient control overthe cross-linking reaction because the reactive groups combine with thepolymer at similar rates, and a three-dimensional network is formed.

A disadvantage with the modification of polymeric materials, such as thecross-linking of cellulosic textiles to improve their properties, isthat the modification must generally be carried out as a last step ortreatment to which the polymeric material is subjected. For example, ifthe cellulosic fibers are cross-linked prior to conversion to yarn, oryarns prior to conversion to fabrics, or even fabrics prior to dyeing,serious difficulties are encountered in subsequent processing steps. lfa cellulose solution (e.g., viscose") is reacted with a polyfunctionalcross-linking agent, the resulting gel can no longer be spun into fiberby conventional and most economical means. If cellulosic fibers arecross-linked by reacting with a cross-linking agent, their elongation atthe breaking point is severely reduced and the resulting fiberstherefore difficult to spin into yarns. Because of the foregoingdifficulties, the cross-linking modification of the fibers is usuallycarried out as a final step after the end product, such as the textilefabric, has been formed, and usually after the dyeing of the fabric.Also, because of the foregoing difficulties, the usefulness of thecrosslinking processes is limited, their scope restricted, and themodification of the cellulosic fibers must be carried out by the fabricfinishers and not by the fiber manufacturers, as would be desirable insome instances.

In connection with the manufacture of garments, it is often advantageousand desirable to obtain creased or pleated fabrics. However, it is notcommercially feasible to introduce creases or pleats in finishedgarments by carrying out the known cross-linking reactions while thegarment is in a pleated or creased configuration. Nor is it economicallypossible to cut and manufacture garments from fabrics which have alreadybeen creased in some areas.

It is also frequently desirable to obtain permanently crimped yarns bycarrying out a cross-linking reaction while the yarns are in asuper-twisted state, but processing of the yarns in this manner is verydifficult.

Accordingly, it is an object of this invention to obviate the presentdisadvantages and limitations existing in the use of known modifying orcross-linking agents for polymers.

It is an object of this invention to provide a process for modifyingpolymeric materials containing active hydrogen atoms by first reactingthe materials at any stage of their manufacture with one reactive groupof an unsymmetrical, polyfunctional modifying agent, in order to attachthe agent to the materials and subsequently during the same or differentstage of manufacture, reacting another but different reactive group ofthe agent with an active hydrogen atom of the material 'so as toeffectively cross-link the material and thus modify its properties. Forthe purpose of the following specification and claims, we define asactive hydrogen any reactive hydrogen atom which is capable of beingadded to, being replaced by, or entering into reaction with thefunctional group of the reagent employed.

It is a further object of this invention to provide a process formodifying polymeric materials having active hydrogen atoms by reactingthe materials with an unsymmetrical modifying agent having functionalgroups of different reactivity on the molecule, wherein one functionalgroup reacts with an active hydrogen of the polymeric material under oneset of reaction conditions and the other reactive group reacts with anactive hydrogen of the polymeric material under a different set ofreaction conditions.

It is another object of this invention to provide a process formodifying polymeric materials containing active hydrogen atoms byreacting the materials with a modifying agent containing polyfunctionalunsymmetrical reactive groups which react at widely different ratesunder the same reactive conditions whereby one functional group is firstattached to the polymeric material and subsequently, the secondfunctional group is attached to the polymeric material to effectivelycrosslink the polymeric material and thus modify its properties.

It is another object of this invention to provide a process forimparting desirable properties to cellulosic fabrics including improvedwet and dry crease recovery properties by the stepwise reaction of anunsymmetrical bifunctional cross-linking agent with the cellulosicfibers at any stage of fiber processing.

Another object of the invention is to provide a polymen having anunsymmetrical bifunctional crosslinking agent attached thereto as theresult of reaction between an active hydrogen atom of the polymer andone of the functional groups of the agent whereby the physicochemicalproperties of the polymer, such as a cellulosic material, remainsubstantially the same as those of an untreated polymer, and the changein properties does not occur until the other functional group of thecross-linking agent is reacted with another active hydrogen atom of thepolymer and the agent becomes in effect a cross-link.

It is another object of this invention to provide new and usefulpolyfunctional cross-linking agents for treating polymeric materialsincluding cellulosic materials.

Another object of this invention is to provide processes for forming theaforesaid new and useful polyfunctional cross-linking agents.

A further object of this invention is to provide polymeric materialshaving an unsymmetrical polyfunctional compound attached thereto by thereaction of one functional group with an active hydrogen of thematerial, which treated polymeric material is capable of further andsubsequent reaction between the remaining functional groups and otherhydrogen atoms of the material whereby the properties of the materialmay be modified by such subsequent reaction.

It is a further object of this invention to provide a method ofcross-linking cellulosic fibers by treating the cellulosic material witha bifunctional compound under one set of reaction conditions wherein onefunctional group of the compound reacts with the cellulosic material,and subsequently subjecting the treated cellulosic material to adifferent set of reaction conditions wherein the second functional groupof the compound reacts with the cellulose to modify the properties ofthe cellulosic material.

It is a further object of this invention to provide a process for themanufacture of garments which are permanently creased or pleated fromfabrics containing reactive side chains by completing the cross-linkingreaction while the finished garment is in the desired configuration.

It is a further object of this invention to provide a process for thepreparation of reactive sizing and pigment binder materials whereby saidmaterials are reacted with a difunctional compound to link onefunctional group of said compound with the materials and subsequentlysubjected to curing to achieve insolubilization of said materials on atextile fabric.

It is still a further object of this invention to provide a process forobtaining a permanently crimped yarn by completing the crosslinkingreaction while yarn containing reactive side chains is in asuper-twisted configuration and thereafter detwisting the yarn.

ln attaining the objects of this invention one feature resides inmodifying a polymeric material containing active hydrogen atoms byreacting the material with an unsymmetrical bifunctional modifying agenthaving one functional group reacting with the active hydrogen atoms ofthe polymeric material under exceedingly mild conditions and otherreactive group entering into reaction with the active hydrogen atomswhen heated to a temperature of at least 100C. in the presence of asuitable catalyst. Alternatively, one functional group of the reagentcan be inert under alkaline conditions and react with the activehydrogen atoms of the polymeric material under acidic conditions, whilethe second functional group reacts under alkaline conditions, so that astepwise reaction can be achieved by providing acidic and alkalineconditions of catalysis in separate steps.

A specific feature resides in having the unsymmetrical polyfunctionalcross-linking agent of the invention contain at least one reactive groupwhich is reactive at ambient temperatures with the active hydrogen atomsof cellulose and in having the cross-linking agent contain anotherreactive group which is an activated oxyethyl group which reacts athigher temperatures, so that substantially complete control over themodification process can be achieved.

Other objects, features, and advantages of the invention will be moreapparent from the following disclosure of the invention.

To modify or cross-link polymers having active hydrogen atoms, thepolymers are reacted with an unsymmetrical polyfunctional compound ofthe formula wherein Q is an organic radical, X is a functional group andY is a functional group which differs from X in structure andreactivity. The reaction takes place under conditions whereby only onefunctional group reacts with an active hydrogen of the polymer, andsubsequently the treated polymer is subjected to a set of reactionconditions wherein the other functional group of the compound reactswith still another active hydrogen of the polymer. When the polymer is acellulosic material, the compound XQ-Y can be attached to the cellulosemolecules by reaction of the functional group X with the hydrogen in ahydroxyl group of the cellulose molecule under a particular set ofreaction conditions. To cross-link the cellulosic material, the treatedmaterial is subjected to the particular reaction conditions which enablethe functional group Y to react with an active hydrogen of the cellulosemolecules. Alternatively, the reaction conditions may be the same but Xand Y have the properties of reacting at widely different rates undersuch conditions.

It has been found that excellent results are obtained when a polymericmaterial having active hydrogen atoms is' treated with an unsymmetrical,difunctional modifying agent having the formula:

in which a. R is selected from the group consisting of hydrogen, loweralkyl and lower acyl, b. R is selected from the group consisting ofhydrogen and lower alkyl,

c. A and A are selected from the group consisting wherein R is selectedfrom the group consisting of substituted and unsubstituted alkyl andaralkyl radicals,

d. Z is a bivalent organic radical selected from the group consisting ofalkylene, aralkylene, the residue of a diamine in which Y is a divalentorganic radical and R has the same definition as above, the residue of aheterocyclic diamine in which the two nitrogen atoms are part of theheterocyclic ring D, the residue of a substituted or unsubstitutedhydrazine radical:

and a nitrogenous residue wherein R has the same meaning as above.

e. n is either 0 or 1,

f. R is a member selected from the group consisting RI RI in which A isselected from the group consisting of a polar residue derived from areagent of weak nucleophilic character and the aziridinyl residueswherein R in each of the formulas has the meaning defined above, namely,a member selected from the group consisting of hydrogen and lower alkyl.

Representative compounds coming within the definition of Formula Iinclude CH OCH CH CON CH OCH CH COHNCH NHCOCH=CH cn cu CH2 CH CH CH CHOCH CH SO NHCH CH NHSO CH=CH CH OCH CH COCH COCH=CH CH COOCH CH SO CH=CHll CH OCH CH SCH CH N CH CH COOCH CH SO N Other compounds, particularlythose wherein Z is any one of a large number of alkylenes, aralkylenes,and diamine residues, will be apparent to those skilled in the art asbeing satisfactory cross-linking agents for the process of theinvention.

It has been further found that a polymeric material having activehydrogen atoms, such as cellulosic material, can also be modified bytreating it with the new and novel sulfone and sulfonamide compounds ofthe invention having the formula wherein R, R and R, Z and n have thesame definitions as in Formula (I).

Furthermore, excellent results have been obtained with new and novelsulfone compounds having the formula wherein R and R have the samedefinition as above and R' is a member selected from the groupconsisting of CH=CH and --CH CH A wherein A is a member selected fromthe group consisting of a polar residue derived from a reagent of weaknucleophilic character and an aziridinyl group having the formulawherein R has the same definition as above.

Best results occur when the lower alkyl groups referred to in the'aforesaid formulas l and II, or which form a part of the lower acylgroup, contain 1 6 carbon atoms and, preferably, when they contain from1 4 carbon atoms.

Among the polar residues (A) which can be present in the compoundsrepresented by the formulas (I) and (II) as well as (ll-a) are groupsderived from reagents of weak nucleophilic character. More specifically,the polar residues are selected from the group consisting of the anionof a strong acid (ionization constant and the cation of a weak base(ionization constant 10 Specific examples of A are the following: When Ais the anion of a strong acid:

OSO M sulfate residue, where M is selected from the group consisting ofalkali and ammonium SSO M thiosulfate residue, where M has the samemeaning as above OCOCH acetate residue, and the like. When A is thecation of a weak base: 5 N C H pyridinium 3 NCH benzyl dirnethylammoniumCHZCGH5 -N C l-l isoquinolinium l0 N C l-l picolinium, and the like.

Nucleophilic character is defined as the tendency to donate electrons orshare them with a foreign atomic nucleus. (Gilman, Organic Chemistry,Second Edition, Vol. II, p. 1859.)

The reaction of the new' unsymmetrical compounds with cellulosic fibersis significant since processes for cross-linking the cellulose moleculesimpart many highly desirable properties to textile materialsmanufactured from cellulosic fibers. The present invention will beillustrated by the reaction of the unsymmetrical sulfones of the aboveformulas with cellulosic materials, including cotton fabrics andregenerated cellulosic fabrics, and cellulose acetate (containingresidual hydroxy groups) although it must be understood that thecompounds of generic formula (I) can be used as stepwise modifying orcross-linking agents for all polymeric materials containing a pluralityof active hydrogen atoms per polymeric molecule, both cellulosic andnon-cellulosic, which polymeric materials include natural fibrouspolymers such as cellulose, wool, silk, and the like; synthetic fibrouspolymers such as polyamides, polyvinyl alcohol fibers, and the like;natural nonfibrous materials such as starch, gelatin, and the like; andsynthetic non-fibrous polymers such as polyvinyl alcohol resin,polypeptides, and the like. It is to be further understood that theaforesaid polymeric materials having active hydrogen atoms may bereacted at any stage of their development including as solutions, asfibers, as yarns, as textile fabrics and the like with one of thefunctional groups of the modifying agent, and, subsequently, at anotherstage of development, the treated polymeric material is reacted underconditions such that another different functional group of the modifyingagent reacts with the polymeric material so as to effect a cross-linkingof the polymers and the formation of a three-dimensional network ofpolymers joined or cross-linked by the modifying agent. Thus, theunsymmetrical polyfunctional modifying agent can be attached by one ofthe functional groups to the polymeric material in fiber form and, afterthe fiber has been converted to yarns and subsequently to a fabric, thefabric may be subjected to the proper reaction conditions which permitthe other functional group on the modifying agent to react with anactive hydrogen on the fabric polymer and effect cross-linking, thusmodifying the properties of the fabric. As is apparent from the above,it is necessary that the material being treated include polymers havingactive hydrogen atoms and thus the process of the invention is alsoapplicable to blends of polymeric materials containing the activehydrogen atoms with materials having no active hydrogens, includingfabrics made from a blend of two or more fibrous polymers.

As further illustrative of the invention, the difunctional compounds ofFormula I can be reacted with an active hydrogen containing polymericmaterial such as viscose solutions or cellulose acetate solutions(containing residual hydroxyl groups) prior to converting are thosehaving the formula the polymer into the fiber form. At this point one ofthe I functional groups of the compounds of Formula I re-(HMROCHZ(I:HSOQCH=CH2 acts and is linked to the active hydrogen of thepoly- 1 mer. The polymer solution is then spun by conventional 5 h R l df h means into the fiber and the cross-linking reaction may m w Se ectemm t 6 group consisimg of hybe completed on the fiber, yam or afterweaving the drogen, lower alkyl and lower acyl, and R 18 selected fabricy curing. from the group consisting of hydrogen and lower alkyl;

The process of this invention can also be carried out and to introducepermanent creases or pleats in finished 10 2 2 2 2 garments. By carryingout the cross-linking reaction I with the compounds of Formula l in astepwise manner R it is possible to attach the reactant to the fiber,yarn or in which R and R have the same definition as shown fabric bystable chemical bonds at an early stage of proabove and A is selectedfrom the group consisting of a cessing. Then after the fabric has beenmade up into polar residue derived from a reagent of weak nuelcothefinished garment, permanent creases and pleats can philic character;such as the cation of a weak base (e.g. be introduced by completing thecross-linking reaction -N 5 5, py 0f the anion Of a Strong acid on thefinished garment creased, pleated or otherwise (e.g., SSO Na,thiosulfate; OSO -,Na, sulfate) as deshaped in the desiredconfiguration. The final crossscribed above. linking reaction can becarried out by the tailor or retail The compounds shown in Formulas Illaand Wu are shop by simple means such-as heating or pressing,characterized by the presence of the beta-oxyethyl sul- The reactantsand processes of the invention can be fonegrouping which is capable ofentering into reacused to obtain twisted or false-twisted cellulosicyarns tion with active hydrogen atoms only under essentially by carryingout the first stepof a cross-linking reaction anhydrous conditions andat elevated temperatures. employing the compounds of Formula I at anydesired They are further characterized by the presence of the stage, andcompleting the crosslinking while the yarn is vinyl sulfone grouping(Formula Illa) and the correin a super-twisted state. The first step ofthe modificasponding saturated derivative grouping ACl-l Cl-ltion,namely reaction of one reactive functional group 50 (Formula lVa) whichare capable of entering with the molecules of the fiber or yarn, can becarried into reaction with active hydrogen atoms in the presout at themost convenient stage of manufacture. ence of water and at ambienttemperature. These new Thereafter the second functional group can bereacted compounds can be attached to polymers containing acin a simplemanner in order to set the super-twisted tive hydrogen atoms, as shownin the following equaconfiguration after appropriate mechanicaltreatment. tions wherein the symbol Pol-H is used to designate a Afterthe cross-linking reaction is completed, the yarn polymer moleculecontaining a plurality of active hymay be subjected to a detwistingoperation whereby a drogen atoms.

MOH 2) PolH AcH,CH,so,CHcH,oR Pol-( H. .CH SO. .CHCH MA H O permanentlytexturized yarn is obtained. In the second reaction, MOH represents analkali A further application for the reactant and processes metalhydroxide, such as sodium hydroxide or a basic of this invention is inthe preparation of reactive pigcompound of equivalent strength.

ment binders and sizing compounds. By means of the The reactionsillustrated by the foregoing equations compounds of Formula I it ispossible to introduce side can be carried out at ambient temperature inthe preschains into such soluble polymeric materials as starch, ence ofwater under conditions which do not remove or polyvinyl alcohol and thelike without affecting their affect the beta-oxyethyl sulfone grouping.Such polysolubility properties. The modified polymer can then mericreaction products can be converted to end prodbe applied to varioustextiles, cellulosics and nonucts which can be cross-linked at anydesired stage of cellulosic in nature, which are thereafter subjected toprocessing by effecting reaction of the beta-oxyethyl a curing reactionwhereby the reactants are cured in sulfone with unreacted polymermolecules as shown in situ to achieve insolubilization of the polymericmaterithe following equation:

R1 V R1 als. When such reactive sizes are applied to non- The foregoingreaction takes place when the polycellulosic fabrics theinsolubilization takes place by meric product is heated to ,atemperature of about cross-linking of the polymer itself. In the case oftreat- 100C. In the presence of a suitable catalyst. Thus, as

ment of cellulosic fabrics, achemical reaction producwill be readilyapparent, cross-linking of polymeric ing the cross-linking can also takeplace between the chains canbe carried out on the modified polymer atmodified polymer and the textile itself. any desired time.

lncluded among the novel compounds of Formula I The compoundscorresponding to Formulas llla and Na in which R and R are hydrogen canbe prepared It is also possible to convert the [3 hydroxyethyl, B -albythe following reactions: koxyethyl sulfoxide or sulfone shown above tothe corresponding sulfated products by employing sulfating 4 g g agentssuch as sulfamic acid, chlorosulfonic acid, or H4 $9 3 H'ILHQSO-LHZCHZC' 5 sulfur trioxide as shown in equations (5 b) and (5 c) below,where M represents the cation of the base embewhydruxyelhy'bemhydwxyehylbem ployed in the neutralization of the sulfuric acidester.

sulfone chlorethyi sulfone The crosslmkmg reaction of the unsymmetricaldiv I functional compounds, such as those of Formulas Illa HSOZCHZCHLMOH HO( H4 H2504 H4 HZA 0 and lVa, with polymeric materials, and moreparticu- A represents the residue derived from a reagent of larly withcellulose, can be carried out in two distinct weak nucleophiliccharacter, MOH is preferably an aland completely controllable steps. Inthe first step, the kali metal hydroxide, but any alkaline compoundhavgroup SO CH==CH or, alternatively, -SO CH C- ing a dissociationconstant greater than about 10 will H A, is reacted at ambienttemperatures in the presbe satisfactory in the aforesaid reaction. enceof an aqueous alkali to form a side chain the poly- As is evident fromthe foregoing equation, the bismer. thepolymer. In the case ofcellulose, some cellubeta-hydroxyethyl sulfone in the presence of a SOClis lose molecules are converted to a cellulose ether havconverted tobeta-hydroxyethyl-beta' chloroethyl suling the formula fonel When thelatter compound is reacted with a suitable reagent such as an alkalimetal thiosulfate, the fol- CellOCH CH SO CHCH-,R lowing compound lSformed: RI w v HOCH CH SO Cl-l Cl-l SSO Na When thebeta-hydroxyethyl-beta' chloroethyl sul- This ether can then be reactedwith another cellulose fone is reacted with pyridine, it forms apyridinium molecule in aseparate step to form across-linked prodchloridederivative, having the following formula: 40 uct as shown by thefollowing equation:

9} (6a)CeIlOH+CelIOCH CH SO EIHCH OR Likewise, thebeta-hydroxyethyl-beta' chloroethyl v R] sulfone can be reacted withother compounds to convert it to other saturated derivatives of polarcharacter.

The compounds corresponding to Formulas llla and Ce|'OCH2CH25O1CHCH-:0ClVa in which R is a lower alkyl or lower acyl group and R is hydrogen orlower alkyl, can be prepared by the +ROH I,

following reactions:

SOCl: HSCH CH OH UWROCHfiHOl-l ROCH CIHCl ROCH HSCH CH OH R SOCI H OROCH CIHSCH C (l 2H O ROCH CHSOCH CH OH R I R, l

'lH O H 0 SOC]: ROCH CHSO CH CH CI ROCH CHSO CH CH 0H L. l ,Ll MOH ROCHCHSO CH=CH The foregoing reaction can be carried out at tempermoved toform a thioether chain. The following equaatures of about 100C. orhigher in the presence of a tion illustrates the reaction employingcellulose as the mild alkaline catalyst under conditions which allow thepolymeric material.

removal of the byproduct molecule ROH by evaporation (when R is eitherhydrogen or lower alkyl) or by 16cl(ell0H+ROCH ("H-S-CH=(Hneutralization (when R is acyl).

Further included among the novel compounds of R! Rm cellocHkcHflscHcHzokFormula I are sulfonium compounds having the forl mula:

The thioether linkage is not a strong activating group, ROCH2CH"5CH=(7H:and before completing the cross-linking reaction it is Li L...preferable to increase the reactivity of the modified polymer byoxidizing the thioether side chain to the in which R and R have the samemeaning as previously corresponding sulfoxide or sulfone. This can beeasily defined above, and R is a member selected from the accomplishedwith common oxidizing agents such as group consisting of substituted andunsubstituted alkyl hydrogen peroxide, as shown in the followingequation and aralkyl radicals; and

in which R and R have the same meaning as previously llvb ROCHQCH"SCH2CHZA"' 20 CeIIOCH CHL SCHCH OR CellOCH CH SOCHCH 0R RI Rm R I R lcenocmcn smcncn oiz defined above, R has the same meaning as in FormulaIIlb above, and A is selected from the group consisting of a polarresidue derived from a reagent of Th ulf xide or sulfone reactionproduct can be weak nucleophilic character. Some of the compoundsreadily cross-linked in presence of an alkaline catalyst shown informulae Illb and IV b can be prepared for exat elevated temperature aspreviously shown in equaample by the following sequences of reactionstion (6a)'above.

R'" halide RI [Ll Rn] l SOCL: l, Sulfation RI Rlll ase Examples ofsuitable R'" groupings in the unsymmet- Also included among the novelcompounds of the inrical sulfonium compounds of formulae (Illb) andvention are the following: (lVb) above are the following:

Methyl, ethyl, propyl, butyl and generally unsubsti- R tuted alkyl; L

Cyanoethyl, alkoxy alkyl and generally alkyl groups containing inertsubstituents; (VH) ROCHZCHSOZCHZCHZN Benzyl, methyl benzyl, phenylethyl, and generally aralkyl groups which are unsubstituted or containinert substituents. L

When the unsymmetrical sulfonium compounds shown in formulae (111 b) and(IV b) are reacted with in which R is selected from the group consistingof hy-' a polymer containing active hydrogen (e.g. cellulose) drogen,lower alkyl and lower acyl, R is a member sein presence of an alkalinecatalyst, a side chain is lected from the group consisting of hydrogenand lower formed. Depending on reaction conditions, the group alkyl. Thecompounds of formula VII can be prepared R" may remain attached to thesulfur atom or be reeither from the compounds of formula Illa byaddition of a three-membered heterocyclic imino compound as shown by wayof example in equation (7a).

or they can also be prepared by reacting the correspondingbeta-haloethyl sulfonyl compounds with three-membered heterocyclic iminocompounds under suitable reaction conditions.

Further compounds included in generic formula (1) are thosecorresponding to formula (Vlll) below.

(Vlll) ROCH CH CONHCH NHCOCH=CH which can be obtained for example simplyby the addition of one mole of alcohol to one mole of the symmetricalunsaturated compound N,N methylene bis acrylamide, and related compoundsprepared in similar manner from bis acrylamides and his vinylsulfonamides of other bis secondary and bis primary amides, Otherunsymmetrical compounds included in generic formula (l) can be obtainedby suitable preparative methods. For example, a compound containing twoNH- groups (e.g., hydrazine, aliphatic diamines, heterocyclic diaminesand the like) can be acylated with two different reactants as shown inthe following equations, in which Y, R and R have the same meaningpreviously defined above and b can be 1 or zero.

CH --CHCOCI Similar reactions are employed when the compound containingthe two NH groups is a heterocyclic compound m HNDNH in which the twonitrogen atoms are part of the heterocyclic ring D.

Still another class of unsymmetrical reactants can be prepared byacylation of amides, as shown for example in the following equations:

wherein R and R have the same meaning as previously defined above.

Also included are unsymmetrical ketones such those shown in formulas(IX) and (lXa) below;

(lX) ROCH CH COCH COCH=CH (lXa) ROCH CH COCH COCH CH A in which R and Ahave the meaning specified previously. The unsymmetrical ketones offormulas (IX) and (lXa) can be prepared for example as shown in equation(8).

cH cHcooU-t,

The unsaturated compounds shown in the foregoing formulae and asreaction products in the foregoing equations can be converted to othernew and useful un symmetrical cross-linking agents by a reaction withthree-membered heter'ocyclic imino compounds analogous to the reactionshown in equation (7a) for the unsymmetrical sulfone compounds.

Included among the compounds of generic formula (I) are alsounsymmetrical aziridinyl compounds correand prepared by reacting thecyclic imino with the appropriate acid halide as shown in equations (9)and 10) (for the chloride) in the presence of a suitable It is apparentfrom the above discussion that a large number of unsymmetrical reagentscoming within the scope of the generic formula (I) are included in thescope of the present invention. For some compounds, for example those inwhich the grouping R is grouping R is where A is aziridinyl or those inwhich the grouping R is aziridinyl the two steps of the cross-linkingprocess are both carried out at elevated temperature, but one functionalgroup is reacted under alkaline conditions, while the second is reactedunder acidic conditions.

Thus, the processing conditions required to carry out the stepwisecross-linking employing the unsymmetrical reagents of the presentinvention depend on the chemical structure of the reagent selected.

The following examples are merely illustrative of the features of theinvention, but are not to be considered limiting in any manner withrespect to the scope of the invention.

EXAMPLE 1 Preparation of 2 chloroethyl 2'hydroxyethyl sulfone 154 grams1 mol) of anhydrous bis-(2 hydroxyethyl) sulfone were dissolved in 500g. of dimethyl ether of ethylene glycol and 79 g. (1 mol) of pyridinewere added thereto. 95 g. (0.8 mol) of thionyl chloride were then addedwith stirring and cooling. The temperature was maintained at 40-45C. andthe addition took 50 minutes. The mixture was then refluxed for 30minutes at 82-85C.

The reaction mixture was poured into water, and the organic phase wasseparated. The organic phase wasthen dried over Na SO and the solventwas removed by distillation, leaving 66 grams of crude product in theform of a brown liquid.

Analysis:

- Total chloride: 17.7% (determined by hydrolysis) Free chloride: 2.48%(determined by AgNO titration) Bound chloride: 15.22% (by difference)EXAMPLE 2 Preparation of 2 hydroxyethyl sulfonyl ethyl pyridiniumchloride 69 grams (0.4 mol) of 2 chloroethyl 2'hydroxyethyl sulfone, 32'grams (0.4 mol) of pyridine, and grams of isopropanol were refluxed withstirring at 8892C.

for 12 hours. A tan solid precipitated in the course of reaction,indicating that essentially all of the organic chloride which waspresent was converted to ionic chloride. The solvent layer was decanted,and the precipitate was washed with acetone and ether on a filter.

'6 1' grams oflight tan crystalline product were obtained.

Analysis: Chloride found: 14.25% (By AgNO titration) Calcd. chloride:14.10% Equivalent weight:

found 248 calcd. 251.5 The equivalent weight was determined byelectrometric titration with standard NaOH solution (end pt: pH 10.5).

EXAMPLE 3 Preparation of 2 methoxyethyl chloride grams (2.5 mols) of 2methoxyethanol and 216 grams (2.75 mols) of pyridine were diluted with100 grams of ethylene glycol dimethyl ether. 327.8 grams 2.75 mols) ofthionyl chloride were then added with stirring over a period of twohours. The temperature was maintained below 50C. by means of a coolingbath. After addition of the SOCI; the mixture was heated to reflux andstirred at 80-85C. for 30 minutes. The reaction mixture was poured on to1,000 g.

of crushed ice and the water layer was separated. The

EXAMPLE 4 Preparation of 2 methoxyethyl 2' hydroxyethyl sulfide Cl-lOC1-l Cl-l SCH Cl-1 OH chloride was filtered off, and ethanol and waterwere removed by stripping under reduced pressure. The product was thendistilled. Bp: 104lO7C. at 6 mm. The distillate was a colorless liquid.

Analysis: percent sulfur found: 23.2%; calcd. 23.5%. The distillateobtained weighed 381 grams, corresponding to a yield of 80 percent ofthe theoretical.

EXAMPLE Preparation of 2 methoxyethyl 2 hydroxyethyl sulfone. CH OCH CHSO CH CH OH 200 grams (1.47 mols) of 2 methoxyethyl- Z'hydroxyethylsulfide (product of example 4) were charged in a reaction vessel, and 2grams of 85 percent phosphoric acid were added. 137 grams (1.41 mols) of35 percent aqueous hydrogen peroxide were added dropwise with stirringover a period of 90 minutes and the temperature was maintained below55C. by means of a cooling bath. The mixture was then heated to reflux,and another portion of 137 grams of 35 percent hydrogen peroxide wasadded over a period of 60 minutes at 100107C. The mixture was thenrefluxed for 12 hours or until a test for residual hydrogen peroxide wasnegative. The water was removed under reduced pressure at 17 mm to a pottemperature of 105C.

The product was obtained as a light yellow liquid which weighed 200grams and contained only a very small amount of oxidizable sulfur(0.25%). The yield was 81.5 percent of the theoretical.

EXAMPLE 6 Preparation of 2 methoxyethyl 2chloroethyl sulfone. CH OCH CHSO CH CH Cl 50.4 grams (0.3 mol) of 2 methoxyethyl 2'hydroxyethylsulfone (product of example 5) were dissolved in 26 grams (0.33 mol)'ofpyridine, and 39.3 grams (0.33 mol) of thionyl chloride were addeddropwise while stirring, over a period of 60 minutes at a temperaturenot exceeding 40C. The mixture was heated to 70C. and kept at 70C. for30 minutes. After cooling to room temperature, the reaction mixture waspoured on to a saturated sodium chloride solution (in water), andextracted with dimethyl ether of ethylene glycol three times using 100ml. of the ether for each extrac tion. After separating and drying theorganic phase, the solvent was removed under reduced pressure, and theresidue was distilled. v Bp: 13 l-132 at mm. The product was a pale.yellow liquid obtained in 40 percent yield. Analysis:

Bound chloride: found 18.9%

calcd. 19.05% Methoxyl content: found 16.65

calcd. 16.62

EXAMPLE 7 Preparation of 2 methoxyethyl sulfonyl ethyl pyridiniumchloride 200 grams (1.07 mols) of 2 methoxyethyl- 2chloroethyl sulfone(product of example 6) were mixed with 250 grams of isopropanol andgrams (1.07 mols) of pyridine, and refluxed for 6 hours at 8090C., atwhich time essentially all of the organic chloride present was convertedto ionic chloride. The isopropanol was removed under reduced pressure,and the crystalline residue was washed with acetone and ether on afilter.

The weight of the white crystalline product so obtained was 262.8 grams,corresponding to a yield of 91 percent of the theoretical.

Analysis:

Chloride content: found 12.2%

calcd.- 13.3% Equivalent weight: found 288 'calcd.- 266.5

The equivalent weight was determined by electrometric titration with astandard NaOH solution.

EXAMPLE 8 Preparation of 2 methoxyethyl, 2thiosulfatoethyl sulfone.

CHgOCHgCHgSOgCHgCHgSSOaNZ 93.2 grams (0.5 mol) of 2 methoxyethyl2chloroethyl sulfone (product of example 6) were mixed with 93 grams ofethanol, and a solution of 124 grams (0.5 mol) of sodium thiosuifatepentahydrate in 124 grams of water was added. The mixture so obtainedwas refluxed with stirring for 4 hours, until essentially all of theorganic chloride was converted to ionic chloride. The reflux temperatureof the mixture was 8090C. After the refluxing, percent conversion wasachieved, as indicated by titration for free thiosulfate ion. Thereaction product was not isolated in crystalline form, but the ethanolwas distilled off and the residual aqueous solution was analyzed asfollows:

Calculated concentration of product from the weight of aqueous solutionobtained: 42.8%.

Concentration determined from the amount of sodium hydroxide consumed inalkaline hydrolysis: 43.1percent.

Concentration determined from the amount of sodium thiosulfate liberatedin alkaline hydrolysis with sodium hydroxide: 39.9 percent.

EXAMPLE 9 Preparation of 2 methoxyethyl vinyl sulfone 46.6 grams (0.25mol) of 2 methoxyethyl 2' chloroethyl sulfone (product of example 6)were added dropwise with continuous stirring to a solution containing26.0 grams (0.25 mol) of triethylamine and 100 grams of ethylene glycoldimethyl ether. External cooling was necessary in order to maintain thetemperature at 25-30C. The addition required 40 minutes. An additionalhour of stirring at room temperature was necessaryto reach 80%conversion after the addition of the chloride was completed. Thetriethylamine hydrochloride which precipitated was filtered off and thesolvent was removed under reduced pressure. The residue was vacuumdistilled. Bp: 96-98C. at 1 mm. Yield of dis- EXAMPLE 10 Preparation of2 hydroxyethyl vinyl sulfone 125.0 grams (1.23 mols) of triethylaminewere added dropwise with continuous stirring to a solution containing172.5 grams (1.0 mol) of 2 chloroethyl 2'hydroxyethyl sulfone (productof example 1) in 500 grams of dioxane. External cooling was necessary inorder to maintain the temperature at 3035C. The addition required 60minutes. An additional hour of stirring at room temperature wasnecessary to reach 95 percent conversion after the addition oftriethylamine was completed. The pH of the reaction mixture was adjustedto 6.8 by adding glacial acetic acid. Then the triethylaminehydrochloride which precipitated was filtered off and the solvent wasremoved from the filtrate under reduced pressure. The residue was vacuumdistilled. The product was collected as a fraction of b.p. 1 14-119C at0.3 mm. The yield of distilled product was 50.5 grams corresponding to37.2 percent of the theoretical. n 1.5005. Vinyl content 17.4% (calcd.:19.8%).

EXAMPLE 1 1 Preparation of the Na salt of 2 methoxyethyl sulfonylethylsulfate.

A. Preparation of the ammonium salt 168 grams (1 mol) of 2 methoxyethyl2' hydroxyethyl sulfone (product of example 5), 101 grams (1 mo1+ 5%excess) of sulfamic acid and 17 grams of urea were charged in a reactionvessel. The mixture was heated to 1001 C.: when the reaction becameexothermic, the source of external heat was removed and the temperaturewas maintained between 1 -125C. by cooling as needed. When the reactionceased to be exothermic the temperature was maintained between 120-125C.with external heating for 60 minutes.

The crude product obtained was dispersed in ether and filtered. Afterfiltration and drying 237.5 grams of white crystalline product wereobtained. Yield: 89.5%. M.p. 96-99C. Equivalent weight determined by nonaqueous electrometric titration with standard alcoholic Na methylatesolution: 292 (calcd.: 265). B. Preparation of the Na salt 237 grams(0.9 mol) of 2 methoxyethyl sulfonylethyl ammonium sulfate (product ofexample 11 A) were dissolved in 500 grams of distilled water and thesolution was allowed to pass through an ion exchange column whichcontained 1,500 ml. wet Amberlite 1R-1201-1 resin* (*Product of the Rohmand Haas Chemical Co.). The column was washed with an additional 500 ml.of distilled water. A sample of the combined solutions obtained (whichweighed 1158 grams) was titrated with standard NaOH solution. Conversionto free acid was 100 percent. The entire solution was then neutralizedwith 48.0 grams of anhydrous Na CO to pH 5.8.

The concentration of the solution was determined by the consumption ofNaOH of the reagent and found to be 18.2% (equivalent to a 92.5 percentyield).

A crystalline product could be isolated from the solution by strippingand triturating with acetone. M.p. 7480C. Eq. wt. 290 (calcd. 270).

EXAMPLE 12 Preparation of 2 methoxyethyl 2' aziridino ethyl sulfone. CH2

H;,C0CH2CH2SO2CHL,CH3N

29.0 grams (0.19 mol) of 2 methoxyethyl vinyl sulfone (product ofexample 9) were added to 13.2 grams (0.3 mol) of ethylene imine keepingthe temperature at .29"30C. by cooling with an ice bath. The time of theaddition was 25 minutes, and stirring for 60 minutes at room temperatureafter completing the addition was sufficient to achieve completereaction. The excess ethylene imine was distilled off and the residualyellow liquid weighed 35.1 grams. The equivalent weight determined bytitration with standard acid was 208 (calcd.: 193). The equivalentweight determined by thiosulfate titration (described in JACS 77,5918-22 (1955) was 21 1. The yield of product was 88.6 percent of thetheoretical.

EXAMPLE 13 Preparation of 2 methoxypropionamidomethyl acrylamide CH OCHCH COHNCH NHCOCH=CH 42.1 grams of 60 percent aqueous N-methylolacrylamide (0.25 mol) and 14.0 grams of 37 percent aqueous HClwere added dropwise at room temperature to a solution of 51.5 grams of2-methoxypropionamide (0.5 mol) in 50 grams of water. The mixture wasthen stirred for 1 hour, and allowed to stand at room temperatureovernight. The reaction mixture was then cooled to 5C. and neutralizedto pH 6.0 by the gradual addition of Na CO The white crystallineprecipitate formed was filtered, and twice recrystallized fromisopropanol. Mp. l55-157C.

Vinyl content'( determined by dodecyl mercaptan titration) 13.65%(calcd. 14.55%): methoxyl content 17.05% (calcd. 16.65%); nitrogencontent 15.22% (calcd. 15.05%). Mixed mp. with methylene bis acrylamide:98-110C. Mixed mp. with methylene bis-methoxypropionamide (mp. 146-149C)125-.135C.

EXAMPLE 14 A. Preparation of 2-methoxyethyl 2"hydroxyethy1 ethylsulfonium bromide.

CH CH OCH A mixture of 136 grams 1.0 mol) of 2-methoxyethyl2'hydroxyethyl sulfide (product of example 4) and of 125 grams (1.0 mol)of 2-bromoethanol was refluxed for 40 hours until the reflux temperaturerose to 7273C. conversion was achieved. The crude product obtained had abromide ion content of 29.0 percent (calcd. 30.6%).

B. Preparation of the Inner Salt of 2-Methoxyethy1- 2'ethyl, ethylsulfonium 56.0 grams (0.48 mol) of chlorosulfonic acid were addeddropwise with continuous stirring to a mixture containing 104 grams(0.40 mol) of 2-methoxyethyl Z'hydroxyethyl ethyl sulfonium bromide(product of example 14 A) and 500 ml. chloroform. During the additionthe temperature was maintained between so obtained weighed 827 grams andcontained 98 grams of the desired product.

The foregoing are merely illustrative of the processes whereby the newand novel compounds of the'invention may be formed. The reactionconditions will vary depending upon the particular compound to beproduced. Thus, in Examples 2,7 and 8 the reaction occurs at atemperature of from 80 to 90C. in a period of from 4 14 hours and thereactants are present in equimolar proportions. In Example 12, on theother hand, the imine is present in excess and'the reaction is conductedat low temperatures of 2930C. and then completed at room temperature.Variations in temperature and times will be readily apparent.

Whereas the chlorine derivative is utilized as an intermediate inseveral of the foregoing examples, it is to be understood that any ofthe halogen derivatives will operate satisfactorily.

EXAMPLE 15 Reaction of the Inner Salt of 2 methoxyethyl 2'sulfatoethylethyl sulfonium with Cotton Cellulose A. Samples of 80 X 80 cotton werepaddedwith an 11 percent aqueous solution of the product of example 14Bat 100 percent wet pickup to give 0.11 gram of reagent per gram offabric and dried at 80-90C. One

sample (1) was then padded with a 3.0 percent aqueous Both samples wererolled wet, wrapped in polyethylene sheeting and allowed to stand for 30min. at room temperature. After this reaction period, the fabrics wererinsed in a 1 percent acetic acid solution, then washed in detergentsolution at 6070C rinsed in water, dried and conditioned to determineweight increase.

B. The physical properties of the fabrics were determined and thesamples were then treated with a 3.0 percent aqueous hydrogen peroxidesolution for 60 min. at room temperature. After drying at 80C., the- 7samples were treated with a 3.0 percent solution of potassiumbicarbonate, dried at -90C., cured for 3 min. at C. and washed. Thechange in physical properties resulting from treatments (A) and (B) wasas follows:

TABLE 1 After oxidation and heating (Step B) Sample Sample Sample Sample1 11 l 11 Weight increase over untreated 3.0 2.83 Sulfur content 0.580.58 Dry Crease Recovery Angle (W F) 191 223 205 Wet Crease RecoveryAngle (W F) 192 195 230 227 Warp Tensile Strengthflb.) 57 56 44 46 WarpTear Strength (11).) 1.6 1.6 1.4 1.4

EXAMPLE 16 Reactions of 2-hydroxyethyl sulfonylethyl pyridinium chloride(product of-example 2) with Cotton Fabric A. A sample of cotton fabric(known as 80 X 80 print cloth) was impregnated with a 25 percent aqueoussolution of the product of example 2 on a laboratory padder, setting therolls at such a pressure as to give a 100 percent wet pickup. 0.25 gramof reagent were thus deposited on each gram of cotton fabric. Theimpregnated fabric was framed to the original dimensions and dried in aforced draft oven at 8090C., then treated by padding with a 5.5 percentsodium hydroxide solution. The amount of NaOl-l solution picked up bythe fabric was such (76%) as to yield a 1.04 mols ratio of NaOH toreagent on the fabric. The fabric was rolled and allowed to stand wet atroom temperature for 60 min. care being taken to prevent evaporation ofwater by covering the roll with polyethylene or other nonporousmaterial. The fabric was rinsed with 1 percent acetic acid to neutralizeresidual NaOH, and washed at 60-70C. The reaction described yielded a3.6 percent increase in fabric weight forming the product Cel loCH Cl-lso Cl-l Cl-l ol-l.

The sulfur content of the fabric so treated was equivalent to theobserved weight increase. The physical properties of the treated cottonfabric (crease recovery, tensile strength, tear strength) wereessentially identical with thos of the untreated fabric, since in themodification of the fiber only one reactive grouping of the reagent wasinvolved and side chains were intro-.

duced without incipient cross-linking or formation of athree-dimensional network.

B. The second reactive gropuing (beta-oxyethylsulfonyl) of themodifiedcotton product described in example 16(A) could be reacted withthe residual unmodified cellulose molecules by the procedure describedbelow. The modified cotton fabric prepared in example 16(A) wasimpregnated by padding with a 0.5

percent aqueous solution of potassium bicarbonate, dried at 8090C., thencured for 3 minutes at 150C., washed and dried. The catalyzed heatingstep efficiently effected cross-linking, as shown for example by thefollowing changes in physical properties:

TABLE it Before heating After heating The crease recovery angle wasdetermined by the method described in the Technical Manual of theAmerican Association of Textile Chemists and Colorists, 1960 edition,pp. 165-167, Tentative Test Method 66-1959, ASTM designation D 1295-53T.

It is apparent from the results given above that the properties of thecotton fabric (as illustrated for example by the crease recovery angle)were not significantly altered by the first step (A) of the reaction,while they were greatly improved by the cross-linking reaction whichtook place in the second step (B).

EXAMPLE l7 Reactions of 2 methoxyethyl sulfonylethyl'pyridinium chloride(product of Example 7) with Cotton Fabric A. Samples of 80 X 80 printcloth were padded with 40 and 20 percent solution of the product ofexample 7 to give 36.6 and 18.4 percent reagent, based on the weight ofthe dry fabric, respectively. The samples were dried and padded withNaOH according to the procedure of example 16A. The mol ratio of NaOH toreagent was thus 1.19 and 1.19 respectively. The samples were rolled,wrapped in polyethylene sheeting and allowed to stand at roomtemperature for 30 minutes. After the reaction was completed, thefabricswere rinsed in a 1 percent acetic acid solution then washed in adetergent solution at 6070C., rinsed in cold water, dried, conditionedand weighed analytically to determine the weight increase due totreatment.

B. The physical properties of the fabrics were determined and then thefabrics were aftertreated with a 3 percent solution of potassiumbicarbonate, dried at 80C. and cured for 3 minutes at 150C. Routinerinse and wash followed the curing step and the changes in physicalproperties were determined.

The results obtained by the procedures described in 17(A) and 17( B) aresummarized below.

7 TABLElIl Untreated Before heating control example 17(A) After heatingexample 17(B) step produces massive changes in fabric properties, thechanges being proportional to the number of side chains present (asindicated by the weight increase) and capable of entering into thecross-linking reaction.

EXAMPLE 18 Reactions of 2 methoxyethyl thiosulfatoethyl sulfone (productof Example 8) with Cotton Fabric A. A sample of 80 X 80 cotton printcloth was padded with an aqueous solution of the reagent to give 0.2gram of reagent per gram of fabric, and dried at 8090C. The fabric wasthen padded with a 4% NaOH solution at 75.5 percent wet pickup, giving0.03

gram of NaOH per gram of fabric. This was equivalent to 1.08 mols ofNaOH per mol of reagent. The wet fabric was rolled, wrapped inpolyethylene sheeting and allowed to stand for 30 minutes at roomtemperature. After this reaction period, the fabric was rinsed in a 1percent solution of acetic acid, then washed in detergent solution at60-70C., rinsed in water, dried, conditioned and weighed to determinethe weight increase.

B. The physical properties of the fabric were determined and the fabricwas then treated with a 3% solution of potassium bicarbonate, dried at8090C., cured for 3 minutes at- 150C. and washed. The change in physicalproperties resulting from treatments (A) and (B) was as follows:'

TABLE IV Before heating After heating Example 18(A) 1 Example 18(8) 1:Weight increase over untreated 3.15

, Dry Crease Recovery Angle (W F) 171 244 Wet Crease Recovery Angle (W+F) 180 246 Warp Tensile Strength (1b.) 59 39 Warp Tear Strength (lb.)1.6 1.0

EXAMPLE 19 potassium hydroxide at 95 percent wetpickup, giving It isagain apparent that the introduction of side 5 (6.5 percent) weightincreases, while the cross-linking a 1.15 mol ratio of KOH to reagent onthe fabric. The fabric was rolled, wrapped in polyethylene sheeting andallowed to stand wet at room temperature for 30 minutes. It was thenneutralized in 1 percent acetic acid, washed, dried, conditioned andweighed.

B. The physical properties were determined, and the fabric was thentreated with a 1 percent solution of potassium bicarbonate, dried at90C., and cured for 3 minutes at C. After washing, the change inphysical properties resulting from cross-linking was determined. Thechanges in physical properties were essen-' tially nil after step (A),but very considerable after step (B).

EXAMPLE 20 Reactions of Z-methoxyethyl sulfonylethyl pyridinium chloride(product of Example 7) with Regenerated TABLE V Before After Untreatedheating heating Rayon Example Example 20(A) 20( B) 7: Weight increase7.4

Sulfurcontent 0 1.9 1.9 Methoxyl content 0 1.8 Dry crease recovery angle(W F) 203 188 220 Wet crease recovery angle (W F) 181 182 278 Warptensile strength (1b.) 51 43 3 1 Warp tear strength (1b.) 3.2 2.1 1.2

EXAMPLE 21 Reactions of Z-methoxyethyl 2'aziridinoethyl sulfone (productof example 12) with Cotton Fabric.

Samples of 80 X 80 cotton print cloth were padded with the followingaqueous solutions on a laboratory padder: Solution (A) containing 15percent of the product 0 example 12 3.9% KHCO 4 Solution (B) containing15% of the product of example 12 7.8% KHCO Solution (C) containing 7.5%of the product of example 12 3.9% KHCO The wet pickup was 95 percent forsolutions (A) and (B) and 88 percent for solution (C) corresponding to14.2 and 6.6% reagent respectively, based on the weight of the fabric.The samples were dried at 50C. and cured for 3 minutes at 150C, thenthoroughly washed with distilled water. The weight increase for theabove samples was: for sample (A), 7.9% (67% yield); (B), 7.4%; and (C),4.0% (73% yield). After this treatment the cellulose contained the sidechain reaction product cu, cenocn cn so ci-i cnm which exhibited greatlyenhanced crease recovery over the side chain reaction product formed inthe alkali catalyzed first step.

EXAMPLE 22 Reactions of 2-methoxyethyl sulfonylethyl pyridinium chloride(product of example 7) with cottonand rayon A. Cotton yarn skeins werepadded'with a 25 percent aqueous solution of a methoxyethylsulfonylethyl pyridinium chloride (the product of example 7) to give19.95 percent reagent based on the weight of yarn. After drying at80-90C., the skeins were padded with a 5 percent solution of NaOl-l togive 5.25% NaOH based on the weight of the yarn. The mol ratio of NaOHto reagent was thus 1.75. The skeins were wrapped in polyethylenesheeting and allowed to stand at room temperature for 30 minutes. Theywere then rinsed in 1 percent acetic acid and washed in a non-ionicdetergent solution at 6070C., rinsed in cold water, conditioned andweighed analytically to' determine the weight increase due to thetreatment. The yarn skeins were knitted into tubing which was thenpadded with 5 a 3% KHCO, solution, dried at 80C. and cured-for 3minutes'at 150C. Routine rinse and wash followed the curing step and thechanges in physical properties were determined.

8. Rayon yarn skeins were padded with a 25 percent solution ofmethoxyethyl sulfonylethyl pyridinium chloride (product of example 7).After drying at 8090C., the skeins were padded with a 6 percent solutionof KOl-l. The mol ratio of KOl-l to reagent present on the yarn was1.35. The skeins were wrapped in polyethylene sheeting and allowed tostand at room temperature for 30 minutes. After this reaction period,the skeins were rinsed in 1 percent acetic acid and washed in anon-ionic detergent solution at 60-70C., rinsed, dried, and weighedanalytically to determine the weight increase.

The treated skeins were knitted into tubing, padded with a 3 percentsolution of KHCO dried at 80C., and cured for 3 minutes at 150C. Routinerinse and wash followed the curing step and the changes in the physicalproperties of the yarn were determined.

The following table summarizes the changes in physical propertiesobserved as a result of the treatments described in examples 22(A) and22(8).

TABLE v Tensile Strength Yarn Sample Elongation Grams Cotton, untreated4.9 312 Cotton, side chain reacted (Ex. 22(A) before knitting) 5.0 278Cotton, cross-linked (Ex. 22(A) yarn from knitted cured fabric) 3.7 188Rayon, untreated 10.7 289 Rayon, side chain reacted (Ex. 22(8) beforeknitting) 10.7 244 40 Rayon, crosslinked (Ex. 22(B) yarn from knittedcured fabric) 10.8 237 EXAMPLE 23 Reactions 'of Z-methoxyethylsulfonylethyl pyridinium 5 chloride (Product of Example 7) with Cotton QA. A sample of 1.5 inches Pirna cotton fiber was carded to give a websuitable for padding treatment. The web was encased in Dacron polyestersheeting and padded with a 25 percent solution of Z-methoxyethylsulfonylethyl pyridinium chloride (product of example 7) to give percentreagent on the weight of fiber. After drying at 8090C. the web waspadded with a 5 percent solution of NaOH to give 7.5% NaOI-l on theweight of the fiber. The mol ratio of NaOH to reagent present on thefiber was 1.1. The fiber sample was wrapped in polyethylene sheeting andallowed to stand at room temperature for 30 minutes. After this reactionperiod, the fiber web was rinsed in 1 percent acetic acid, then washedin warm water, rinsed and dried. The cotton fiber was processed withoutdifficulty by carding again, drawing, spinning at 7,500 RPM andknitting. The knitted fabric so obtained was padded with a 3 percentsolution of KHCO dried at 80C. and cured for 3 minutes at 150C. Routinerinsing and washing followed the curing step, and the physicalproperties of the yarn manufactured from the treated fiber weredetermined before and after the cross-linking step which was carried outafter knitting.

TABLE Vll Tensile Strength Sample Elongation Grams Cotton yarn preparedfrom untreated fiber (control) 7.9 349 Cotton yam prepared from sidechain reacted fiber (Ex.23A) 6.6 276 Cotton yarn removed from knittedcured fabric (Ex. 23A) 5.0 179 B. An attempt was made to obtain resultscomparable to those outlined in example 23(A) by cross-linking cottonfiber in a single step, and subsequently converting the treated fiberinto yarn and knitted fabric. For this purpose, a sample of the same l.5inches Pima cotton fiber used in example 23(A) was carded to give a websuitable for padding treatment. The web was encased in Dacron polyestersheeting and padded with an aqueous solution containing 6 percentbis(beta hydroxyethyl) sulfone and 3.9% KHCO as catalyst. 10 percentcross-linking agent was deposited based on the weight of the cottonfiber.

After drying at 8090C., the web was cured at 150C. for 3 minutes.Routine rinse and wash followed the curing. An attempt was made toprocess the trated fiber sample into yarn and knitted fabric by theprocedure described in Example 23(A). The carding did not presentunusual difficulties, but the drawing resulted in an unsatisfactory webwhich had a flaky appearance from fibers dispersed throughout. Spinningof this web into yarn was extremely difficult. Even when the spindlespeed was dropped from 7,500 RPM (which was the speed used in Example23(A)) to 5,500 RPM, the end would not stay up for any length of time.Some yam was spun with great difiiculty, but it was so weak that itcould not be knitted.

The experiments described in Example 23 illustrated the great advantageof the invention, namely the possibility of introducing a cross-linkingreagent into fiber, prior to processing, by reacting one functionalgroup only, and without altering the behavior of the fiber inprocessing, and completing the crosslinking reaction at =2 99ers? sta eeihensnsfa ty n P es a- EXAMPLE 24 Reaction of 2-methoxyethyl vinylsulfone with Viscose Solution 2-Methoxyethyl vinyl sulfone (MVS productof TABLE IX Before After Step B Step B %Weight increase over untreated3.0 I 96 Sulfur content 0.57 0.55 36 Methoxy content 0.58 0.36 DryCrease Recovery Angle (W F) 184 245 Wet Crease Recovery Angle (W F) 186237 Warp Tensile Strength (1b.) 56 38 an aqueous solution of the productof example 9 to give 0.08 gram of reagent per gram of fabric. Withoutdrying the fabric was then padded with a 1.3% NaOI-l solution saturatedwith Na SO The wet fabric was rolled, wrapped in polyethylene sheetingand allowedto stand for 60 minutes at room temperature. After thisreaction period, the fabric was rinsed in a l percent solution of aceticacid then washed in detergent solution at 6070C, rinsed in water, dried,conditioned and weighed to determine the weight increase.

B. The physical properties of the fabric were determined and the fabricwas then treated with a 3.0 percent solution of potassium bicarbonate,dried at 80-90C., cured for 3 minutes at 150C. and washed. The change inphysical properties resulting from treatments (A) and (B) was asfollows:

Warp Tear Strength (1b.)

EXAMPLE 26 Reaction of 2-Methoxyethyl vinyl sulfone with RegeneratedCellulose (viscose rayon) Fabric When the procedures of example 25 wererepeated employing viscose rayon challis fabric instead of cotton printcloth, 0.! gram of'the product of example 9 per gram of fabric wasdeposited by padding from an aqueexample 9) was mixed with samples ofviscose solution which had anestimated cellulose content of 7.5 percent.

After various reaction times at room temperature the modified cellulosepolymer was precipitated in dilute H solution, washed with water,neutralized with Na CO solution, thoroughly washed and dried in a vacuumdesiccator.

The following results were obtained in this experiment:

Reaction of Z-Methoxyethyl vinyl sulfone with Cotton Fabric oussolution. After completing the treatment, the following results wereobtained:

EXAMPLE 27 Reaction of 2-Methoxyethyl vinyl sulfone with Filament RayonYarn Samples of filament rayon yarn (Type 1173 American Enka 300/60 2.1S and Type 1141 American Enka /30 2.55 S) knitted into tubes were paddedwith an aqueous solution of the product of example 9 to give 0.20 and0.1 1 gram of reagent per gram of yarn.

Without intermediate drying the samples having 0.20 gram of reagent pergram of yarn were padded with 3.0% KOH solution saturated with Na,SO andthe samples having 0.11 gram of reagent per gram of yarn were paddedwith 1.5% KOl-l solution saturated with Na SO The samples were wrappedin polyethylene sheeting and allowed to stand wet at room temperaturefor 30 minutes. They were then neutralized in 1 percent acetic acid,washed and dried.

The sulfur content of the samples was as follows:

Type 1141 Reaction of the Na Salt of Z-Methoxyethyl sulfonylethylsulfate with Cotton Fabric.

A. A sample of 80 X 80 cotton print cloth was padded with a 24 percentaqueous solution of the product of example 1 1 at 100 percent wet pickupso as to deposit 0.24 gram of reagent per gram of fabric and dried in aforced draft oven at 80-90C. The fabric was then padded with a 4.2%solution of NaOH saturated with NaCl. The wet pickup was 104 percent,giving 0.043 gram of NaOl-I per gram of fabric. This was equivalent to1.22 mols of NaOH per mol of reagent on the fabric.

' After the NaOH treatment, the wet fabric was rolled smoothly on arubber core, wrapped in polyethylene she'eting and allowed to stand for30 minutes at room temperature. After this reaction period, the fabricwas rinsed in a 1 percent aqueous solution of acetic acid, then washedin detergent solution at 60,-70C, rinsed in water, dried, conditionedand weighed to determine the weight increase.

B. The physical properties of the fabric were determined and the fabricwas then treated by padding with a 3 percent solution of potassiumbicarbonate, dried at 8090C, cured for 3 minutes at 150C and washed. Thechanges in physical properties resulting from treatments (A) and (B) aretabulated below.

TABLE Xl Before After Untreated Step Step Weight Increase over Untreated4.79 Dry Crease Recovery Angle (W F) 146 179 254 Wet Crease RecoveryAngle (W F) 167 182 252 Warp Tensile Strength lb.) 58 54 33 Warp TearStrength (lb.) 1.9 1.6 1.1 Sulfur 0.0 0.80 0.77 OCH; 0.0 0.85 0.32

EXAMPLE 29 Reaction of the Na Salt of Z-Methoxyethyl sulfonylethylsulfate with Rayon Fabric A. A sample of conditioned and weighed rayonchallis fabric was padded with a 25 percent aqueous solution of theproduct of example 11 at 120 percent wet pickup to give 0.30 gram ofreagent per gram of fabric, and dried at 8090C. The fabric was thenpadded with a 5.7% KOH solution saturated with NaCl at 130 percent wetpickup giving 0.074 gram of KOH per gram of fabric. This was equivalentto 1.14 mols of [(01-1 per mol of reagent. The wet fabric was rolledsmoothly on a rubber core, wrapped in polyethylene sheeting and allowedto stand for 30 minutes at room temperature. After this reaction period,the fabric was rinsed in a 1 percent aqueous solution of acetic acid,then washed in detergent solution of 60-70C., rinsed in water, dried,conditioned and weighed to determine the weight increase.

B.The physical properties of the fabric were determined and the samplewas then treated by padding with a 3% aqueous solution of potassiumbicarbonate, dried at 8090C., cured for 3 minutes at 150C... and washed.The changes in physical properties resulting from treatments (A) and (B)were as follows:

TABLE Xll Before After Untreated Step Step Weight Increase overUntreated 7.78 Dry Crease Recovery Angle (W F) 191 216 257.

32 Wet Crease Recovery Angle (W F) 135 176 264 Warp Tensile Strength(lb.) 44 40 31 Warp Tear Strength (lb.) 3.5 2.2 1.4 Sulfur 0.0 1.45 1.48OCH, 0.0 1.65 0.90

EXAMPLE 30 Reaction of the Na Salt of 2-methoxyethyl sulfonylethylsulfate with Spun Rayon Yarn A. A sample of 19.5/1 denier spun rayonyarn was knitted into tubing. The tube was padded with an aqueoussolution of the product of example 1 1 to give 0.36 gram of reagent pergram of yarn and dried at 8090C. The tubing was then padded with a 6%KOH solution saturated with NaCl at 142 percent wet pickup, giving 0.081gram of KOl-l per gram of fabric. This was equivalent to 1.13 mols ofKOH per mol of reagent on the fabric. The wet knitted fabric was rolled,wrapped in polyethylene sheeting and allowed to stand for 30 minutes atroom temperature. After this reaction period, it was rinsed in a 1percent solution of acetic acid then washed in detergent'solution at6070C., rinsed in water, dried, conditioned and weighed to determine theweight increase.

B. The knitted tubes were de-knitted, prepared for weaving, and wereused as filling yarn for a fabric in which the warp was /34/52 semi-dullnylon yarn.

The filling physical properties of the fabric were determined and thefabric was then treated by padding with a 3 percent solution ofpotassium bicarbonate,

dried at -90C, cured for 3 minutes at C and washed. The change in thephysical properties resulting from the alkaline catalyzed heat treatmentwere as follows:

TABLE X111 Before After Heating Heating Weight Increase (knitted tube)7.48 Dry Crease Recovery Angle (Filling) 82 104 Filling Tensile Strength(lbs.) 42 37 Filling Tear Strength (lbs.) 6.5 5.6 I: Sulfur (fillingyarns) 1.63 1.49 OCH, (filling yarns) 1.60 1.05, Filling shrinkage (5Launderings Tumble Dried) EXAMPLE 3] Reaction of the sodium salt of2-methoxyethyl sulfonylethyl sulfate with Cotton Fiber.

A sample of 1% inches Pima cotton fiber which was previously scoured ina dilute NaOl-l solution to remove waxes and other non cellulosiccontaminants was carded to give a web suitable for padding treatment.The web was padded with a 42 percent aqueous solution of the product ofexample 11 at 260 percent wet pickup to give 1.09 grams of reagent pergram of fiber. After drying at 80-90C. the web was padded with a 14percent solution saturated with NaC l to give 0.22 gram of NaOH per gramof fiber. The mol ratio of NaOI-I to reagent present on the fiber was1.36. The fiber was wrapped in polyethylene sheeting and allowed tostand at room temperature for 30 minutes. After this reaction period,the fiber web was rinsed in 1 percent acetic acid solution, washed inwarm water, rinsed and dried in an oven at 80-90C.

Sulfur content of the modified cellulose fiber obtained was 2.59 percentcorresponding to 12 percent weight increase.

EXAMPLE 32 ipsp gttv a tis w 9,.., th.thsse iqm Salt of Z-methoxyethylsulfonylethyl sulfate (product of Example 11) A sample of 80 X 80 printcloth which was treated with the reagent according to the proceduredescribed in example 28 (A), containing 0.80 percent sulfur and 0.85percent methoxyl, was dyed with Atlantic Direct Sky Blue A extra conc.direct dyestuff (color index, Direct Blue 15) to a medium blue shade ona steam bath. After dyeing, the sample was washed in a detergentsolution at 60-70C., rinsed in water and dried.

The shade and depth of the color of the dyed samples were the same asthat of an untreated sample dyed in the same dyebath.

The colorfastness of the dyed fabricswas determined and the fabrics werethen treated with a 3 percent solution of potassium bicarbonate, driedat 8090C., cured for 3 minutes at 150C. and washed.

Before After Heating Heating Colorfastness to Laundering Treated 1 1 3(AATCC Test 3A 160F) Untreated 1 1 This example shows that the dyeingbehavior of the modified cotton fabric before completing thecrosslinking reaction in the heating step is the same as for untreatedcotton fabric. Also, crosslinking increases the colorfastness tolaundering of the direct dye from a rating of l to a rating of 3.

EXAMPLE 33 Permanent Creasing by using Non Volatile Base as Catalyst Asample of 80 X 80 print cloth which was treated with 2-methoxyethylvinylsulfone (product of example 9) according to the procedure describedin example 25(A) and had a weight increase of 4.5 percent over theuntreated fabric and an untreated control sample were treated with 3.0percent solution of potassium bicarbonate, dried at 80C., creased in thewarp direction, ironed for5 minutes with the iron set at 150C.,neutralized with 1 percent solution of acetic acid, rinsed and dried.The physical properties of the samples were as follows:

TABLE xiv Permanent Creasing by using Volatile Base as Catalyst A sampleof 80 X 80 print cloth, which was treated with 2-methoxyethyl vinylsulfone (product of example 9) according to the procedure described inexample 25(A) and had a weight increase of 4.0 percent over theuntreated fabric was treated with a 5 percent aqueous solution oftetraethyl ammonium hydroxide, dried at 80C., creased in the warpdirection and ironed for 5 minutes with the iron set at 150C.

The physical properties of the sample were as follows:

After 1 Laundering Dry Crease Recovery Angle (W F) 190 Wet CreaseRecovery Angle (W F) 244 Crease Retention Rating 5.0

The quaternary ammonium hydroxide catalyst dissociated into volatileby-products during ironing, and washing of the sample to remove the baseafter heating was not necessary. 1

EXAMPLE 35 20.0 grams of corn starch (Corn'Product Co., NY.)

were added to a mixture of 180 grams of dioxane and 10 mls. of 5 Naqueous NaOH, and stirred at room temperature for 10* minutes. 2 gramsof 2-methoxyethyl .vinyl sulfone were added to the slurry and themixture film which was dried at 50C. for minutes then cured for 8minutes at C. in order to effect cross-linking. The cured, cross-linkedstarch could no longer be dissolved in the aqueous NaOH solution (8g/liter NaOH).

EXAMPLE 36 20 grams of polyvinyl alcohol resin (marketed under the tradename of Elvanol 72-60 by E.I. du Pont de Nemours & Co.) were added to amixture of grams of dioxane and 10 mls. of 5 N aqueous NaOH, and stirredat room temperature for 10 minutes. 2 grams of 2- methoxyethyl vinylsulfone were added to the resulting slurry, and the reaction mixture wasstirred for 1 hour then allowed-to stand overnight at room temperature.The slurry was filtered, and the solid was dispersed in a mixture of 60grams of dioxane, 30 grams of water and 10 grams of glacial acetic acidin order to neutralize the residual NaOl-l. After filtering, the solidwas washed repeatedly with a dioxane-water mixture and dried.

1 gram of the modified polyvinyl alcohol product so obtained wasdissolved in a mixture of 9- grams of ethylene glycol and 9 grams ofaqueous NaOH solution (containing 8 g/liter NaOl-l) at 109C. A film wascast from this solution, dried at 60C. for 2 hours and then cured for 8minutes at 150C. After the curing step, the modified (cross-linked)polyvinyl alcohol could no longer be dissolved in the ethyleneglycol-aqueous NaOl-l mixture at 109C.

EXAMPLE 37 tinuous stirring to a solution containing 1.0 gram' NaOl-land 90 mls. of water. 10.0 grams (0.067 mol) of 2-methoxyethyl vinylsulfone (product of example 9) v were added dropwise at room temperatureto the starch suspension. After 1 hour reaction time at roomtemperature, 250 mls. water were added and the pH of the mixture wasadjusted to 3.0 by adding 0.2 N HCl solution. By adding 500 mls. acetonea precipitate was obtained. This was filtered, washed and dried. Themodified starch had a 2.6% S content.

10 grams of the modified starch were boiled in 140 mls. of water for 1hour. The viscous 6.6 percent starch solution was stored for 2 weekswithout any mildew formation and without any change in viscosity.

Under the same conditions, a 6.6 percent viscous solution prepared fromunmodified corn starch showed considerablemildew growth andgelatinization after 6 days.

8. Reaction of Modified Starch with Cotton Fabric A sample of 100percent cotton fabric known as twist twill was padded with an aqueousdispersion containing 4.0 percent modified starch (product of example37(A)) and 3.0% KHCO The wet pickup was 60 percent. Another sample ofthe same fabric was padded with an aqueous dispersion containing 4.0percent unmodified com starch and 3.0 percent KHCO at 60 percent wetpickup.

' Both samples were dried at 80C., cured 3 minutes, and washed. I

The flexural rigidity (average of warp and filling) of the sampletreated with modified corn starch decreased by only 27 percent after lmachine launderings, while the rigidity of the sample treated withunmodified starch decreased by 48 percent.

(Flexural rigidity was measured according to the Cantilever Test Method,ASTM Dl388-55T).

This indicated that chemical bonding of the starch to the fabric hadbeen achieved.

EXAMPLE 38 A. Preparation of Reactive Size from Polyvinyl Alcohol 42.0grams of polyvinyl alcohol Elvanol 71-30, product of E1. du Pont deNemours & Co.) were added slowly to 260 mls. of boiling water withcontinuous stirring. After the viscous PVA solution cooled down, 4.0grams of NaOH dissolved in 20 mls. of water and then 8.4 grams (0.056mol) of 2-methoxyethyl vinyl sulfone (product of example 9) were addeddropwise at room at 150C. for

temperature. After 30 minutes reaction time at room temperature, 250mls.of water were added and the pH of the mixture was adjusted to 3.0 with0.2 N HCl solution. By adding 500 mls. of ethanol, a precipitate wasobtained. This was filtered, washed and dried in a vacuum oven at 40C.The sulfur content of the modified PVA was 2.0 percent.

By adding 10 grams of the modified PVA to 90 mls.

of boiling water with continuous stirring, a homogenous viscous solutionwas obtained. B. Reaction of Modified PVA with Cotton Fabric.

A sample of 100 percent cotton fabric known as twist twill was paddedwith an aqueous dispersion containing 4.0 percent of modified polyvinylalcohol (product of example 38(A)) and 3.0 percent KHCO The web pickupwas 60 percent.

Another example of the same fabric was padded with an aqueous dispersioncontaining 4.0 percent unmodified PVA (Elvanol 31-40) and 3.0 percentKHCO at 60 percent wet pickup.

Both samples were dried at C. and cured at 150C. for 3 minutes.

The overall flexural rigidity of the sample treated with modified PVAdecreased by only 16 percent after l0 machine launderings while therigidity of the sample treated with unmodified PVA decreased by 78.0percent.

(Flexural rigidity was measured by the Cantilever Test Method ASTMDl388-55T).

As is evident from the above eiyamples, the functional 'group RO- of themodifying or cross-linking agent of Formula I reacts with an activehydrogen of the polymers of polymeric material being treated, such ascellulose, at temperatures of about C; or higher, while the R" radicalsC=CH and -CHCHA where A is a polar residue derived from a reagent ofweak nucleophilic character, will react with an active hydrogen atom ofthe polymers at ambient temperatures usually under alkaline conditions.When the R radical of Formula I is either the aziridinyl group or thewherein A is an aziridinyl radical, the R radical will react with anactive hydrogen of the polymers under acidic conditions. Thus, stepwisemodification or crosslinking of the polymers is accomplished in anydesired manner or sequence.

Furthermore, in Formula I, supra, it will be understood that thealkylene group includes methylene, ethylene, butylene, octylene,decamethylene, etc., while the aralkylene group includes Cl-l,C H Cl-l,,

